CN103435033A - Simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave - Google Patents
Simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave Download PDFInfo
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- CN103435033A CN103435033A CN2013103501394A CN201310350139A CN103435033A CN 103435033 A CN103435033 A CN 103435033A CN 2013103501394 A CN2013103501394 A CN 2013103501394A CN 201310350139 A CN201310350139 A CN 201310350139A CN 103435033 A CN103435033 A CN 103435033A
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Abstract
The invention relates to a simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave. The method comprises the following steps: a rolling vibration mill is adopted to grind 150-g normal zinc powder in argon shield for 5 h and seal for standby application; 50 meshes of flake graphite and concentrated nitric acid are mixed according to the mass ratio of 1 to 3, and stirred for 10 minutes at the temperature of 30 DEG C; expandable graphite is obtained after 50 meshes of flake graphite is repeatedly cleaned and filtered, and dried at the temperature of 60 DEG C; after the expandable graphite is treated for 30s in a muffle furnace at the temperature of 900 DEG C, expanded graphite is obtained and sealed for standby application; grinded zinc powder and expandable graphite weighted in proportion are put into distilled water, absolute ethyl alcohol is added and stirred uniformly, ultrasound is performed continuously for 6 to 10 hours in ultrasonic wave, after still standing is performed for 10 minutes, suspended liquid at the upper part is extracted and centrifugally separated, and the graphene based nano-zinc oxide composite material is obtained after vacuum drying is performed at the temperature of 60 DEG C. The method provided by the invention is simple in process, economical and environmental friendly, and can be used for large scale production, the composite material prepared through the method is stable in structure, and the method is important supplement for the preparation method of nano-zinc oxide composite material.
Description
Technical field
The present invention relates to a kind of short-cut method for preparing Graphene zinc-oxide nano rod composite material in ultrasonic wave, belong to the nano material preparing technical field.
Background technology
The research and development of field of nanometer technology is maked rapid progress, and new technology and novel material emerge in an endless stream, yet the basis of everything research is the reliability preparation of nano material.Nano-ZnO, as a kind of semiconductor material of broad stopband, has a wide range of applications in photochemical catalysis, piezoelectric, field of electronic devices.But be limited to certainly as N-type semiconductor and the natural defects such as ,Xin gap, oxygen room, the characteristics such as its optimized light, electricity, magnetic, catalysis can't be applied fully.People are just considering mutually compound its larger potentiality of excavating of nano-ZnO and other materials.At present, consider that the compound report of zinc oxide and Graphene is few, and Graphene is owing to having good conductivity and to light absorpting ability, if thereby prepare a kind of novel material for photoelectric field by zinc oxide and Graphene are mutually compound, will there is larger value.But common complicated process of preparation and the energy consumption of Graphene are large, pollute highly, therefore, find the easy and easy control of a kind of process, cost is low, and make zinc oxide be easy to the preparation method compound with Graphene, the popularization and application of the C-base composte material of nano zine oxide is had great importance.
Summary of the invention
The invention discloses a kind of short-cut method for preparing Graphene-zinc-oxide nano rod composite material in ultrasonic wave, the condition harshness existed to overcome existing technology of preparing, the process complexity, energy consumption is polluted the shortcomings such as large.The inventive method adopts nano level zinc particle and the expanded graphite ground, and directly utilizes ultrasonic technique to prepare Graphene-zinc-oxide nano rod composite material.Process of the present invention is simple, and method is easy, and product is easily controlled.
The present invention is realized by the following technical programs:
A kind of short-cut method for preparing Graphene-zinc-oxide nano rod composite material in ultrasonic wave at first at room temperature, grinds 5h by 150g general industry zinc powder with rolling-vibrating grinding machine in ar gas environment, prepares nano level zinc particle, and sealing saves backup; By 50 order crystalline flake graphites and concentrated nitric acid in mass ratio 1:3 mix, and stir 10min under 30 ℃, repeatedly after cleaning and filtering, 60 ℃ of dryings make expansible black lead, then in retort furnace 900 ℃ process 30s and obtain expanded graphite, seal standby.
Concrete preparation method is as follows:
(1) with electronic scales weighing 0.2～1.0g ground respectively zinc powder and 5g expanded graphite, mix and be placed in 50～75ml distilled water, and add appropriate dehydrated alcohol, rock evenly.Wherein, zinc powder is 1～5:25 with the quality of expanded graphite than scope.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 20～40KHz, power 300W, under natural light, continuous ultrasound is processed 6～10 hours, during took out also and acutely rock 30 seconds every 15 minutes;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) obtain the finished product by precipitating the dry 12h of the vacuum drying oven that is placed in 60 ℃ in (3).
The Graphene made-zinc-oxide nano rod composite material is the surface that the corynebacterium Zinc oxide particles evenly is combined in multilayer or single-layer graphene.
The present invention has simple to operate, process is easily controlled, economic environmental protection, low for equipment requirements, the advantage such as can be mass-produced, control the charge capacity of nano zine oxide on Graphene by the ratio that changes zinc powder and expanded graphite, control the structure of matrix material by changing ultrasonic time and ultrasonic frequency, the Graphene of preparation-zinc oxide nano rod composite structure is stable, to the preparation method who develops nano-zinc oxide composite material, is a kind of important supplementing.
The accompanying drawing explanation
Fig. 1 is embodiment 1, the X ray electron-diffraction diagram (XRD) of sample in embodiment 2 and embodiment 4;
The scanning electron microscope image that Fig. 2 is sample in embodiment 1 (SEM);
The high power transmission electron microscope micro-image (TEM) that Fig. 3 is sample in embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail, but the present embodiment can not be for limiting the present invention, and every employing similarity method of the present invention and similar variation thereof, all should list protection scope of the present invention in.
A kind of short-cut method for preparing Graphene-zinc-oxide nano rod composite material in ultrasonic wave at first at room temperature, grinds 5h by 150g general industry zinc powder with rolling-vibrating grinding machine in ar gas environment, prepares nano level zinc particle, and sealing saves backup; By 50 order crystalline flake graphites and concentrated nitric acid in mass ratio 1:3 mix, and stir 10min under 30 ℃, repeatedly after cleaning and filtering, 60 ℃ of dryings make expansible black lead, then in retort furnace 900 ℃ process 30s and obtain expanded graphite, seal standby.
[embodiment 1]
(1) with electronic scales weighing 0.2g ground respectively nano level zinc particle and 5g expanded graphite, mix and be placed in 50ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 20KHz, power 300W, under natural light, continuous ultrasound is processed 6 hours, during took out also and acutely rock 30 seconds every 15 minutes;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) obtain the finished product by precipitating the dry 12h of the vacuum drying oven that is placed in 60 ℃ in (3).
[embodiment 2]
(1) with electronic scales weighing 0.4g ground respectively zinc powder and 5g expanded graphite, mix and be placed in 60ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 25KHz, power 300W, under natural light, continuous ultrasound is processed 7 hours, during took out also and acutely rock 30 seconds every 15 minutes;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) obtain the finished product by precipitating the dry 12h of the vacuum drying oven that is placed in 60 ℃ in (3).
[embodiment 3]
(1) with electronic scales weighing 0.6g ground respectively zinc powder and 5g expanded graphite, mix and be placed in 65ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 30KHz, power 300W, under natural light, continuous ultrasound is processed 8 hours, during took out also and acutely rock 30 seconds every 15 minutes;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) obtain the finished product by precipitating the dry 12h of the vacuum drying oven that is placed in 60 ℃ in (3).
[embodiment 4]
(1) with electronic scales weighing 0.8g ground respectively zinc powder and 5g expanded graphite, mix and be placed in 70ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 40KHz, power 300W, under natural light, continuous ultrasound is processed 9 hours, during took out also and acutely rock 30 seconds every 15 minutes;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) obtain the finished product by precipitating the dry 12h of the vacuum drying oven that is placed in 60 ℃ in (3).
[embodiment 5]
(1) with electronic scales weighing 1.0g ground respectively zinc powder and 5g expanded graphite, mix and be placed in 75ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 40KHz, power 300W, under natural light, continuous ultrasound is processed 10 hours, during took out also and acutely rock 30 seconds every 15 minutes;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) obtain the finished product by precipitating the dry 12h of the vacuum drying oven that is placed in 60 ℃ in (3).
The X ray electron-diffraction diagram (XRD) that accompanying drawing 1 is embodiment 1, embodiment 2 and example 4 gained samples, be not difficult to find out the diffraction peak of the ZnO phase that all can see the hexagonal wurtzite structure in sample and the diffraction peak of the carbon phase that multi-layer graphene forms.Illustrate that this inventive method has successfully prepared the carbon-based nano zinc oxide composite.
The scanning electron microscope image (SEM) that accompanying drawing 2 is embodiment 1 gained sample can find out that nano granular of zinc oxide is combined in the surface of multi-layer graphene equably easily.
The electron projection MIcrosope image (TEM) that accompanying drawing 3 is embodiment 1 gained sample, can find out, the Graphene matrix presents the structure of individual layer or multilayer, nano zine oxide is corynebacterium, be attached to the surface of Graphene matrix, although be subject to the bombardment of electron beam in the observation process, material sample is still keeping stable intimate-association state, further illustrates this method and successfully prepares Graphene-zinc-oxide nano rod composite material.
Claims (2)
1. a short-cut method for preparing Graphene-zinc-oxide nano rod composite material in ultrasonic wave is characterized in that:
At first at room temperature in ar gas environment, 150g general industry zinc powder is ground to 5h with rolling-vibrating grinding machine, prepare the nano level zinc particle, sealing saves backup; By 50 order crystalline flake graphites and concentrated nitric acid in mass ratio 1:3 mix, and stir 10min under 30 ℃, repeatedly after cleaning and filtering, 60 ℃ of dryings make expansible black lead, then in retort furnace, 900 ℃ of processing obtain expanded graphite in 30 seconds, seal standby; Concrete preparation method is as follows:
(1) with electronic scales weighing 0.2～1.0g ground respectively nano level zinc particle and 5g expanded graphite, mix and be placed in 50～75ml distilled water, and add dehydrated alcohol, rock evenly; Wherein, the mass ratio of nano level zinc particle and expanded graphite is 1～5:25;
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 20～40KHz, power 300W, under natural light, continuous ultrasound is processed 6～10 hours, during took out also and acutely rock 30 seconds every 15 minutes;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water;
(4) obtain the finished product by precipitating the dry 12h of the vacuum drying oven that is placed in 60 ℃ in (3).
2. according to the described a kind of short-cut method for preparing Graphene-zinc-oxide nano rod composite material in ultrasonic wave of claims 1, it is characterized in that: the Graphene made-zinc-oxide nano rod composite material is the surface that the corynebacterium Zinc oxide particles evenly is combined in multilayer or single-layer graphene.
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Cited By (5)
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| CN104891485A (en) * | 2015-06-08 | 2015-09-09 | 哈尔滨工业大学（威海） | Method for preparing nano graphite sheet |
| CN105498689A (en) * | 2015-12-09 | 2016-04-20 | 唐山冀东石墨烯科技发展有限公司 | Graphene loaded nano ZnO/Ag composite material and preparation method thereof |
| CN106517167A (en) * | 2016-10-25 | 2017-03-22 | 成都新柯力化工科技有限公司 | Method for manufacturing graphene nanoplatelets by arranging rotary screw rod in vibrating mill and graphene nanoplatelets |
| CN111040324A (en) * | 2019-12-31 | 2020-04-21 | 深圳第三代半导体研究院 | Composite heat dissipation material for semiconductor and preparation method thereof |
| CN113800476A (en) * | 2021-08-30 | 2021-12-17 | 宁波工程学院 | Ultrasonic preparation method of nano metal oxide |
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| CN106517167A (en) * | 2016-10-25 | 2017-03-22 | 成都新柯力化工科技有限公司 | Method for manufacturing graphene nanoplatelets by arranging rotary screw rod in vibrating mill and graphene nanoplatelets |
| CN111040324A (en) * | 2019-12-31 | 2020-04-21 | 深圳第三代半导体研究院 | Composite heat dissipation material for semiconductor and preparation method thereof |
| CN113800476A (en) * | 2021-08-30 | 2021-12-17 | 宁波工程学院 | Ultrasonic preparation method of nano metal oxide |
| CN113800476B (en) * | 2021-08-30 | 2023-09-12 | 宁波工程学院 | Ultrasonic preparation method of nano metal oxide |
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